CN112585176B

CN112585176B - Novel amine-functionalized polymers and process for their preparation

Info

Publication number: CN112585176B
Application number: CN201980048801.6A
Authority: CN
Inventors: L·L·沙弗尔; S·G·哈兹基里亚科斯; M·R·佩里; D·J·吉尔摩; T·汤姆科维奇
Original assignee: University of British Columbia
Current assignee: University of British Columbia
Priority date: 2018-05-23
Filing date: 2019-05-23
Publication date: 2023-10-24
Anticipated expiration: 2039-05-23
Also published as: JP2021525301A; US11555107B2; EP3797126A1; CA3100853A1; AU2019273133A1; US11795315B2; MX2020012493A; KR20210023879A; JP7448958B2; BR112020023661A2; EP3797126A4; CA3103037A1; WO2019222834A1; EA202092823A1; US20220363786A1; CN112585176A; WO2019222852A1; US20210214542A1

Abstract

The present application relates to amine-functionalized polymers made by Ring Opening Metathesis (ROMP) of amine-functionalized cyclic olefins.

Description

Novel amine-functionalized polymers and process for their preparation

RELATED APPLICATIONS

The present application claims priority from U.S. patent application 62/675,465, filed 5/23 in 2018, the entire contents of which are incorporated herein by reference.

Technical Field

The present application relates to amine-functionalized polymers. More particularly, the present application relates to novel amine-functionalized polymers capable of being made by Ring Opening Metathesis (ROMP) of amine-functionalized cyclic olefins.

Background

Catalytic functionalization of olefins represents a sustainable, efficient method for synthesizing molecules associated with the chemical, pharmaceutical and agrochemical industries. This organic conversion is attractive as a valuable base material that can be economically obtained from relatively inexpensive starting materials. Notably, direct C-H functionalization or hydroaminoalkylation (hydroaminoalkylation) of amines with olefins has been notoriously attenuated due to the fact that polysubstituted amines are now readily available without any protecting/positioning groups or photoinitiators.

It is known in the art that complexes of group 3 (Sc), group 4 (Ti, zr) and group 5 (Nb, ta) metals can act as powerful precatalysts in hydroaminoalkylation reactions. For example, N, O-chelated pyridone tantalum salt based complexes are capable of reacting with sterically demanding internal olefins and facilitating their reaction with secondary anilines. These reactions occur in a 100% regioselective manner, yielding branched products.

Despite the high demands placed on simple and economical processes for synthesizing amine base materials in the chemical, pharmaceutical and pesticide industries, the catalytic systems currently in use still have some known problems. For example, hydroaminoalkylation reactions typically require very high reaction temperatures (> 110 ℃) and considerable reaction times (> 20 hours), and many catalysts are not sufficiently tolerant of these. Furthermore, it is well known that the substrate compatibility of these catalysts is problematic, especially for internal olefins such as cyclohexene and cyclooctene. The fact that an excess of olefin (at least 1.5 equivalent excess) is required to achieve complete substrate conversion remains a challenge.

In the case of catalytic systems, the active species have Ta-NMe ₂ Part of the excess olefins tends to be separated from the released HNMe ₂ And the detrimental side reactions between the olefinic reagents, thereby affecting the stoichiometry of the reaction. TaMe ₃ Cl ₂ The use of (C) has proven successful because the hydroaminoalkylation of amine and olefin substrates is achieved in stoichiometric amounts using this catalyst, but it is noted that TaMe ₃ Cl ₂ Is sensitive to light and temperature and is therefore unsuitable for large-scale industrial processes. Using a similar approachThe method takes Ta-Me complex supported by phosphoramidate as a catalyst, and realizes the addition of 1-octene and 4-methoxy-N-methylaniline at room temperature. Although this catalyst exhibits high reactivity, the phosphoramidate Ta-Me complex actually requires an excess of alkene to fully convert the substrate. To improve the stability of early transition metal complexes, it is possible to add, for example, large alkyl groups (e.g.CH ₂ SiMe ₃ And CH (CH) ₂ CMe ₃ ) The form of the sterically hindered entity complexes to the metal center. Earlier, wilkinson and Schrock describe alkyl tantalum complexes Ta (CH) ₂ SiMe ₃ ) ₃ Cl ₂ And Ta (CH) ₂ CMe ₃ ) ₃ Cl ₂ . However, their activity in hydroaminoalkylation reactions has not been reported in the art.

Martinez et al (Applied Petrochemical Research, 5:19-25) have employed a strategy of Ring Opening Metathesis Polymerization (ROMP) using amine-functionalized hindered cyclooctene monomers followed by hydrogenation to obtain polyethylene-like linear polymers, the key being the introduction of covalently bound functional groups into the backbone. However, the incompatibility between commercially available Grubbs catalysts and monomers bearing unprotected amine functionality, which is often observed, limits the usability of this process, as Grubbs metathesis catalysts deactivate during ROMP of amine-containing cyclic olefin monomers.

Thus, efficient preparation of amine-containing polyolefin materials remains a synthetic challenge.

Disclosure of Invention

The present invention is based in part on the following findings: hydroaminoalkylation of the cycloolefin and subsequent ring opening polymerization and optional hydrogenation produce a functionalized polymer comprising at least one amine group. In various embodiments, the amine groups introduce useful properties such as self-healing, adhesion, and/or antimicrobial properties.

Certain aspects of the invention relate to amine-functional compounds of formula 2:

wherein (- -) represents an optional double bond;

wherein M is ¹ And M ² Each independently is-OH, C with or without substituents _1-15 An alkyl group, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functional end group suitable for ring opening metathesis polymerization;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

Wherein each Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Independently is H, a substituted OR unsubstituted linear OR cyclic alkyl OR alkenyl, a substituted OR unsubstituted aryl, a substituted OR unsubstituted heterocycle, an amine compatible protecting group, -C (=o) R ', OR-C (OR') R, and wherein Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is-CR ¹ R ² -NR ³ R ⁴ ；

Wherein R' and R "are each independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group;

wherein R is ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group, or wherein R ³ And R is ⁴ To form a ring portion, or wherein R ³ And R is ⁴ One of which is with R ¹ And R is ² To form a ring portion;

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

where n is a natural number greater than 1.

In various embodiments, the monomers forming the functionalized compound of formula 2 are linked in a head-to-tail fashion, a head-to-head fashion, a tail-to-tail fashion, or any combination thereof.

Certain aspects of the present invention relate to block copolymers comprising: an amine-functional compound as described above; and polymers formed by free radical polymerization or anionic polymerization, the functional end groups M1 and M2 of the amine-functional compound being the starting points.

A block copolymer prepared, the block copolymer comprising: an amine-functional compound as described above; and at least one additional polymer.

Certain aspects of the invention relate to polymers comprising oligomers of formula 3:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are connected in a head-to-head fashion.

Certain aspects of the invention relate to polymers comprising oligomers of formula 4:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

wherein n and m are natural numbers; and

wherein the monomers are linked in a tail-to-tail fashion.

Certain aspects of the invention relate to polymers comprising oligomers of formula 7:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are joined in a head-to-tail fashion.

Certain aspects of the invention relate to polymers of formula X:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

Wherein each Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Y ¹¹ 、Y ¹² 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Independently is H, a substituted OR unsubstituted linear OR cyclic alkyl OR alkenyl, a substituted OR unsubstituted aryl, a substituted OR unsubstituted heterocycle, an amine compatible protecting group, -C (=o) R ', OR-C (OR') R, and wherein Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is-CR ¹ R ² -NR ³ R ⁴ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are connected in a head-to-head fashion.

Certain aspects of the invention relate to polymers comprising oligomers of formula XI:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are connected in a head-to-head fashion.

Certain aspects of the invention relate to copolymers comprising a mixture of different amine-functional monomer units of formula 6:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

Wherein each Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Independently is H, a substituted OR unsubstituted linear OR cyclic alkyl OR alkenyl, a substituted OR unsubstituted aryl, a substituted OR unsubstituted heterocycle, an amine compatible protecting group, -C (=o) R ', OR-C (OR') R, and wherein Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is-CR ¹ R ² -NR ³ R ⁴ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

wherein the monomer units are linked in a head-to-head fashion, a head-to-tail fashion, a tail-to-tail fashion, or any combination thereof.

Certain aspects of the invention relate to brush copolymers and polymeric bristles (brittles) or polymer brushes comprising a polymer as described above, wherein X ¹ 、X ² 、X ³ 、X ⁴ 、Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ 、Z ⁴ 、R’、R”、R ¹ 、R ² 、R ³ And R is ⁴ As a starting point for subsequent synthesis of the polymeric bristles or brushes.

Certain aspects of the present invention relate to an amine-functionalized polyolefin or polyalkylene, wherein the polyolefin or polyalkylene comprises:

where n is a natural number greater than 1.

Certain aspects of the invention relate to a polyalkylene of formula 5:

Wherein X is ¹ 、X ² 、X ³ And X ⁴ Each independently is H or CH ₃ ；

Wherein Y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Z ¹ And Z ² Each independently is H, a substituted OR unsubstituted linear OR cyclic alkyl OR alkenyl, a substituted OR unsubstituted aryl, a substituted OR unsubstituted heterocycle, an amine compatible protecting group, -C (=o) R ', OR-C (OR') R ";

wherein R is ^a 、R ^b 、R ^c And R is ^d Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group, or wherein R ^b And R is ^a To form a ring portion, or wherein R ^a And R is ^b One of which is with R ^c And R is ^d To form a ring portion;

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

where n is a natural number greater than 1.

In various embodiments, the monomers are joined in a head-to-tail fashion, a head-to-head fashion, a tail-to-tail fashion, or any combination thereof.

Polymers, polyalkylenes, polyolefins, and amine-functionalized compounds as described above are useful as antimicrobial agents. Polymers, polyalkylenes, polyolefins, and amine-functionalized compounds as described above may be used to reduce fouling. The soil may comprise biofouling. The polymers described above may be used as adhesives. The adhesive may be used to adhere to a substrate. The substrate may be Teflon (Teflon), glass or metal.

The polymers, polyalkylenes, polyolefins, and amine-functionalized compounds described above may be used as coatings, compatibilizers, stabilizers, metal scavengers (metal scavengers), films, gaskets, anticoagulants, drug delivery agents, or scavengers. In various embodiments, the scavenger binds contaminants during environmental remediation of a marine environment. In various embodiments, the contaminants comprise oil, plastic particles, or a combination thereof. In various embodiments, the membrane is an electrolyte membrane or a filtration membrane for water purification.

Certain aspects of the present invention relate to substrates coated with polymers, polyalkylenes, polyolefins, and amine-functional compounds as described above.

Other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures.

Drawings

In the drawings illustrating embodiments of the invention,

fig. 1 is a schematic diagram of a general strategy for synthesizing linear polyethylene according to an embodiment of the invention.

FIG. 2 is a diagram depicting the hydroalkylation of cyclooctadiene to obtain an amine-functionalized cyclooctadiene derivative in accordance with an embodiment of the present invention. Weight yield (%) is reported after chromatography.

FIG. 3 is a diagram depicting Ring Opening Metathesis Polymerization (ROMP) to obtain amine-containing polycyclooctenes in accordance with embodiments of the present invention.

FIG. 4a is a graph of mass loss rates (%/min) as a function of temperature for five polymers of the invention, namely, "P1", "P2", "P3", "P4" and "P1H".

FIG. 4b is a graph of mass loss (%/min) as a function of temperature for five polymers of the present invention.

FIG. 5 is a DSC thermogram of five polymers of the present invention.

FIG. 6 shows (a) P1 at 50 ℃; (b) P2 at 30 ℃; (c) P3 at 50 ℃; (d) P4 at 50 ℃; (e) Storage (G') and loss (G ") modulus at 50 ℃ for P1H and complex viscosity (|η| >) (sign).

FIG. 7a is a graph of CDCl at 293K ₃ In the amine-functionalized cycloolefin "M1" according to the invention ¹ H-NMR spectra(300MHz)。

FIG. 7b is a CDCl at 293K ₃ In the amine-functionalized cycloolefin "M1" according to the invention ¹³ C-NMR spectrum (75 MHz).

FIG. 8a is a graph of CDCl at 293K ₃ In the amine-functionalized cycloolefin "M2" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 8b is a CDCl at 293K ₃ In the amine-functionalized cycloolefin "M2" according to the invention ¹³ C-NMR spectrum (75 MHz).

FIG. 8c is a graph of CDCl at 293K ₃ In the amine-functionalized cycloolefin "M2" according to the invention ¹⁹ F-NMR spectrum (282 MHz).

FIG. 9a is a graph of CDCl at 293K ₃ In the amine-functionalized cycloolefin "M3" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 9b is a CDCl at 293K ₃ In the amine-functionalized cycloolefin "M3" according to the invention ¹³ C-NMR spectrum (75 MHz).

FIG. 10a is a graph of CDCl at 293K ₃ In the amine-functionalized cycloolefin "M4" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 10b is a CDCl at 293K ₃ In the amine-functionalized cycloolefin "M4" according to the invention ¹³ C-NMR spectrum (75 MHz).

FIG. 11a is a graph of CDCl at 293K ₃ In the polymer "P1" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 11b is a CDCl at 293K ₃ The solid-state spectrum of the polymer "P1" according to the invention.

FIG. 12a is a graph of CDCl at 293K ₃ In the polymers "P2" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 12b is a CDCl at 293K ₃ The solid state spectrum of the polymer "P2" according to the invention.

FIG. 13a is a graph of CDCl at 293K ₃ In the polymer "P3" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 13b is a CDCl at 293K ₃ The solid-state spectrum of the polymer "P3" according to the invention.

FIG. 14a is a graph of CDCl at 293K ₃ In the polymers "P4" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 14b is a CDCl at 293K ₃ The solid state spectrum of the polymer "P4" according to the invention.

FIG. 15a is a graph of CDCl at 293K ₃ In the polymers "P1H" according to the invention ¹ H-NMR spectrum (300 MHz).

FIG. 15b is a CDCl at 293K ₃ The solid state spectrum of the polymer "P1H" according to the invention.

Fig. 16 is a photographic image of macroscopic self-healing of polymer P1 spheres: (a) dry spheres on PTFE; (B) a sphere just touching; (C) And (D) spheres (D) that no longer exhibit discrete boundaries when pulled apart after 24 hours under ambient conditions (C).

Fig. 17 is a photographic image depicting the adhesive properties of the polymer.

FIG. 18 is a graph showing the effect of the ratio of CAN-1 and P2 monomers in the copolymer on the observed glass transition temperature.

FIG. 19 shows the total curves of storage (G ') and loss (G') moduli and complex viscosities (|eta||) of the polymer P2 at 50 ℃, of the copolymer P (ACN-1-co-P2) at 50 ℃ and of the homopolymer of ACN-1 at 50 ℃.

Detailed Description

Definition of the definition

As used herein, "catalyst" refers to a compound that accelerates a chemical reaction without itself being affected. "catalyst" may be used interchangeably with terms such as "precatalyst", "catalyst system" or "catalytic system". As used herein, "catalyst" includes catalytic intermediates or species formed in situ.

As used herein, "group 5 metal" refers to transition metals listed in the periodic table as group 5 containing d electrons, including transition metals vanadium (V), niobium (Nb), tantalum (Ta), and ≡ (Db).

"hydroaminoalkylation" as used herein refers to the reaction between a secondary amine-containing moiety and an olefin. Catalysts may be generally used to facilitate such reactions.

As used herein, "secondary amine" refers to an amine in which the amino group is directly bound to any two C atoms that are hybridized. The two C atoms in the alpha position of the N atom being sp ³ And (3) hybridization.

As used herein, "olefinic hydrocarbon" or "olefin" refers to an unsaturated hydrocarbon containing one or more pairs of C atoms joined by double bonds.

As used herein, "TOF" refers to "turn-around frequency".

Numerical ranges include the numbers defining the ranges. In this document, the word "comprising" is used as an open term, substantially identical to the phrase "including, but not limited to," and the word "comprising" has a corresponding meaning. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an item" includes more than one such item. Citation of references herein is not an admission that such references are prior art to the embodiments of the present invention. The invention includes all embodiments and variants substantially as described above and with reference to the examples and drawings. Headings, titles, etc. are provided to enhance the reader's understanding of the present document, and should not be construed as limiting the scope of the present invention.

Amine-functionalized cyclic olefins

The present invention relates to amine-functionalized cyclic olefins of formula 1:

wherein:

X ¹ 、X ² 、X ³ and X ⁴ Independently H or CH ₃ ；

Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Each independently is: h is formed; a linear or cyclic alkyl or alkenyl group with or without substituents; with or without substituentsAn aryl group; a heterocyclic ring having a substituent or not; amine compatible protecting groups; -C (=o) R'; OR-C (OR ') R'; wherein Y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is-CR ¹ R ² -NR ³ R ⁴ ；

Wherein R' and R "are each independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group; and

where r=0 or 1 and q=0 or 1, where r+q=0, 1 or 2.

R ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ³ And R is ⁴ Ligating to form a ring portion, wherein R ¹ And R is ² Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Wherein R is ³ And R is ⁴ One of which is with R ¹ And R is ² To form a loop portion. Alternatively, R ³ And R is ⁴ One of which is with R ¹ And R is ² To form a ring portion, in which case R ¹ 、R ² 、R ³ And R is ⁴ The remaining groups are each independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or amine compatible protecting group, as the case may be.

In various embodiments, in the amine-functionalized cyclic olefin, X ¹ 、X ² 、X ³ And X ⁴ Each is H. In various embodiments, in the amine-functionalized cyclic olefin, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, in the amine-functionalized cyclic olefin, X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ . In various embodiments, in the amine-functionalized cyclic olefin, R ¹ And R is ² At least one of which is H. In various embodiments, in the amine-functionalized cyclic olefin, R ³ And R is ⁴ At least one of which is H.

In various embodiments, in amine-functionalized cyclic olefins, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms. In various embodiments, Y ³ is-CR ¹ R ² -NR ³ R ⁴ And: each Y ¹ And Y ² Is H; y is Y ⁵ And Y ⁶ Each is H; or each Y ¹ 、Y ² 、Y ⁵ And Y ⁶ Each is H.

In various embodiments, in amine-functionalized cyclic olefins, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms. In various embodiments, Y ³ is-CR ¹ R ² -NR ³ R ⁴ ，Y ⁴ Is H.

The invention also relates to polymers prepared by Ring Opening Metathesis Polymerization (ROMP) of amine-functionalized cyclic olefins as described above.

The invention is thatAlso relates to polymers prepared by Ring Opening Metathesis Polymerization (ROMP) of a mixture of different amine-functionalized cyclic olefins as described above. In various embodiments, the mixture comprises amine-functionalized cyclic olefins as regioisomers. In various embodiments, the adjacent carbon atom on-CR ¹ R ² -NR ³ R ⁴ The positions of the groups are exchanged between regioisomers.

In various embodiments, the monomer units polymerize head-to-head, head-to-tail, tail-to-tail, or any combination thereof.

In various embodiments, the polymer is hydrogenated to remove double bonds in the polymer.

In various embodiments, the polymer is self-healing. In various embodiments, the polymer has adhesive properties. In various embodiments, the polymer has antimicrobial activity.

The polymers described above are useful as antimicrobial agents. The polymers described above can be used to reduce fouling. The soil may comprise biofouling. The polymers described above may be used as adhesives. An adhesive may be used to adhere to the substrate. The substrate may be teflon, glass or metal.

The polymers described above may be used as coatings, compatibilizers, stabilizers, metal scavengers, films, gaskets, anticoagulants, drug delivery agents or scavengers. In various embodiments, the scavenger binds the contaminant during environmental remediation of the marine environment. In various embodiments, the contaminants include oil, plastic particles, or a combination thereof. In various embodiments, the membrane is an electrolyte membrane or a filtration membrane for water purification.

Amine functional compounds

The invention also relates to amine-functional compounds of formula 2:

wherein (- -) represents an optional double bond;

wherein M is ¹ And M ² Each independently ofIn which the site is-OH, C with or without substituents _1-15 An alkyl group, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functional end group suitable for ring opening metathesis polymerization;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

where n is a natural number.

R ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ³ And R is ⁴ Ligating to form a ring portion, wherein R ¹ And R is ² Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted Heterocyclic or amine compatible protecting groups with substituents. Alternatively, R ³ And R is ⁴ One of which is with R ¹ And R is ² To form a ring portion, in which case R ¹ 、R ² 、R ³ And R is ⁴ The remaining groups are each independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or amine compatible protecting group, as the case may be.

In various embodiments, the monomer units forming the amine-functionalized compound of formula 2 are linked head-to-tail, head-to-head, tail-to-tail, or any combination thereof.

In various embodiments, n is 3 to 1000. In various embodiments, n is 3 to 1000. In various embodiments, n is 3 to 600. In various embodiments, n is 5 to 400.

In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Each is H. In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ . In various embodiments, R ¹ And R is ² At least one of which is H. In various embodiments, R ³ And R is ⁴ At least one of which is H.

In various embodiments, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms. For example, Y ³ is-CR ¹ R ² NR ³ R ⁴ When (1): each Y ¹ And Y ² Is H; y is Y ⁵ And Y ⁶ Each is H; or each Y ¹ 、Y ² 、Y ⁵ And Y ⁶ Each is H.

In various embodiments, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms. For example, Y ³ is-CR ¹ R ² -NR ³ R ⁴ When Y is ⁴ H.

Amine-functional compounds as described above are useful as antimicrobial agents. Amine-functional compounds as described above can be used to reduce fouling. The soil may comprise biofouling. The polymers described above may be used as adhesives. An adhesive may be used to adhere to the substrate. The substrate may be teflon, glass or metal.

The amine-functional compounds described above may be used as coatings, compatibilizers, stabilizers, metal scavengers, membranes, gaskets, anticoagulants, drug delivery agents, or scavengers. In various embodiments, the scavenger binds the contaminant during environmental remediation of the marine environment. In various embodiments, the contaminants include oil, plastic particles, or a combination thereof. In various embodiments, the membrane is an electrolyte membrane or a filtration membrane for water purification.

Polymers of formulas 3, 4 and 7

The invention also relates to a polymer comprising an oligomer of formula 3:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are connected in a head-to-head fashion.

The invention also relates to a polymer comprising an oligomer of formula 4:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are linked in a tail-to-tail fashion.

The invention also relates to a polymer comprising an oligomer of formula 7:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

Wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers; and

wherein the monomers are joined in a head-to-tail fashion.

For the oligomers of formulae 3, 4 and 7, R ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ³ And R is ⁴ Ligating to form a ring portion, wherein R ¹ And R is ² Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine compatible protecting group. Alternatively, R ³ And R is ⁴ One of which is with R ¹ And R is ² To form a ring portion, in which case R ¹ 、R ² 、R ³ And R is ⁴ The remaining groups are each independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or amine compatible protecting group, as the case may be.

While formulas 3, 4 and 7 presently provide that the monomers are joined in a head-to-tail, head-to-head, or tail-to-tail fashion, as the case may be, one of skill in the art will appreciate that the monomers may be joined in any combination thereof.

In various embodiments, in the polymer comprising oligomers of formulas 3, 4, and 7, n+m is 3 to 1000. In various embodiments, n is 3 to 1000. In various embodiments, n+m is 3 to 600. In various embodiments, n+m is 5 to 400.

In various embodiments, in a polymer comprising oligomers of formulas 3, 4, and 7The polymer being composed of-OH, C with or without substituents _1-15 An alkyl group, an aromatic ring with or without substituents, a heterocyclic ring with or without substituents, a functional end group suitable for ring opening metathesis polymerization, or any combination thereof.

In various embodiments, in a polymer comprising oligomers of formulas 3, 4, and 7, X ¹ 、X ² 、X ³ And X ⁴ Each is H. In various embodiments, in a polymer comprising oligomers of formulas 3 and 4, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, in a polymer comprising oligomers of formulas 3 and 4, X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ . In various embodiments, in a polymer comprising oligomers of formulas 3 and 4, R ¹ And R is ² At least one of which is H. In various embodiments, in a polymer comprising oligomers of formulas 3 and 4, R ³ And R is ⁴ At least one of which is H.

In various embodiments, in a polymer comprising oligomers of formulas 3, 4, and 7, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms. For example, when Y ³ is-CR ¹ R ² -NR ³ R ⁴ When (1): each Y ¹ And Y ² Is H; y is Y ⁵ And Y ⁶ Each is H; or each Y ¹ 、Y ² 、Y ⁵ And Y ⁶ Each is H.

In various embodiments, in a polymer comprising oligomers of formulas 3, 4, and 7, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms. For example, Y ³ is-CR ¹ R ² -NR ³ R ⁴ When Y is ⁴ H.

Certain aspects of the invention relate to block copolymers prepared by ring opening metathesis polymerization of: amine-functionalized cyclic olefins as described above; and at least one additional cyclic olefin. The at least one additional cyclic olefin includes norbornene or aromatic amine substituted norbornene.

Certain aspects of the invention also relate to block copolymers comprising: an amine-functional compound as described above; and polymers formed by free radical or anionic polymerization, the functional end groups M of the amine-functional compounds being the starting points.

Certain aspects of the invention also relate to brush copolymers and polymeric bristles or polymer brushes comprising a polymer as described above, wherein X ¹ 、X ² 、X ³ 、X ⁴ 、Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ 、Z ⁴ 、R’、R”、R ¹ 、R ² 、R ³ And R is ⁴ As a starting point for subsequent synthesis of the polymeric bristles or brushes.

Certain aspects of the invention also relate to random copolymers prepared by ring-opening metathesis polymerization of: amine-functionalized cyclic olefins as described above; and at least one additional cyclic olefin. The at least one additional cyclic olefin includes norbornene or aromatic amine substituted norbornene.

The polymers described above may be used as coatings, compatibilizers, stabilizers, metal scavengers, films, gaskets, anticoagulants, drug delivery agents or scavengers. In various embodiments, the scavenger binds contaminants during environmental remediation of a marine environment. In various embodiments, the contaminants comprise oil, plastic particles, or a combination thereof. In various embodiments, the membrane is an electrolyte membrane or a filtration membrane for water purification.

Amine-functionalized polyolefins and polyalkylenes

Certain aspects of the invention also relate to amine-functionalized polyolefins or polyalkylenes, wherein the polyolefins or polyalkylenes comprise:

/>

where n is a natural number greater than 1.

In various embodiments, n is 3 to 1000. In various embodiments, n is 3 to 600. In various embodiments, n is 5 to 400.

Certain aspects of the invention also relate to a polyalkylene of formula 5:

wherein M is ¹ And M ² Each independently is-OH, C with or without substituents _1-15 Alkyl having substituentsOr an unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functional end group suitable for ring opening metathesis polymerization;

wherein X is ¹ 、X ² 、X ³ And X ⁴ Each independently is H or CH ₃ ；

Wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

where n is a natural number greater than 1.

R ^a 、R ^b 、R ^c And R is ^d Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ^b And R is ^a Ligating to form a ring portion, wherein R ^c And R is ^d Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ^a And R is ^b One of which is with R ^c And R is ^d To form a ring portion, in which case R ^a 、R ^b 、R ^c And R is ^d The remaining groups are each, as the case may be, independently H, a substituted or unsubstituted, linear or cyclic alkyl groupOr alkenyl, aryl with or without substituents, heterocycle with or without substituents or amine compatible protecting group.

In various embodiments, R ^b And R is ^a At least one of which is H. In various embodiments, R ^b And R is ^a One of them is H. In various embodiments, R ^b is-CR ¹ R ² -NR ³ R ⁴ Wherein R is ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group.

In various embodiments, the monomer units forming the polyalkylene of formula 5 are linked head-to-tail, head-to-head, tail-to-tail, or any combination thereof.

In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Each is H. In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ . In various embodiments, R ¹ And R is ² At least one of which is H. In various embodiments, R ³ And R is ⁴ At least one of which is H.

Certain aspects of the invention relate to copolymers of formula X:

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and

wherein n and m are natural numbers; and is also provided with

R ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ³ And R is ⁴ Ligating to form a ring portion, wherein R ¹ And R is ² Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group. Alternatively, R ³ And R is ⁴ One of which is with R ¹ And R is ² To form a ring portion, in which case R ¹ 、R ² 、R ³ And R is ⁴ The remaining groups are each independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or amine compatible protecting group, as the case may be.

In various embodiments, the monomer units forming the copolymer of formula X are linked head-to-tail, head-to-head, tail-to-tail, or any combination thereof. In various embodiments, the monomer units are connected in a head-to-head fashion.

In various embodiments, in the polymer of formula X, n+m is 3 to 1000. In various embodiments, n+m is 3 to 600. In various embodiments, n+m is 5 to 400.

In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Each is H. In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, X ¹ And X ³ Each H, X ² And X ⁴ Each is CH ₃ . In various embodiments, R ¹ And R is ² At least one of which is H. In various embodiments, R ³ And R is ⁴ At least one of which is H. In various embodiments, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (2) is substituted with two H atomsAnd (5) a seed. In various embodiments, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms.

wherein (- -) represents an optional double bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

Where r=0 or 1 and q=0 or 1, where r+q=0, 1 or 2.

In various embodiments, the monomer units of formula 6 forming the copolymer are linked head-to-tail, head-to-head, tail-to-tail, or any combination thereof.

In various embodiments, the number of monomer units of formula 6 that form the polymer is from 3 to 1000. In various embodiments, the number of monomer units of formula 6 that form the polymer is from 3 to 600. In various embodiments, n+m is 5 to 400.

In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Each is H. In various embodiments, X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ . In various embodiments, X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ . In various embodiments, R ¹ And R is ² At least one of which is H. In various embodiments, R ³ And R is ⁴ At least one of which is H. In various embodiments, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms. In various embodiments, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms.

Various polyolefins or polyalkylenes as described above may be used as antimicrobial agents. Various polyolefins or polyalkylenes as described above may be used to remove soil. The soil may comprise biofouling. Various polyolefins or polyalkylenes as described above may be used as the adhesive. An adhesive may be used to adhere to the substrate. The substrate may be teflon, glass or metal.

The various polyolefins or polyalkylenes as described above may be used as coatings, compatibilizers, stabilizers, metal scavengers, films, gaskets, anticoagulants, drug delivery agents, or scavengers. In various embodiments, the scavenger binds the contaminant during environmental remediation of the marine environment. In various embodiments, the contaminants include oil, plastic particles, or a combination thereof. In various embodiments, the membrane is an electrolyte membrane or a filtration membrane for water purification.

Substrate board

Certain aspects of the invention relate to substrates coated with a polyolefin or a polyalkyl-alkane, amine functional compound or polymer as described above.

In various embodiments, the substrate reduces biofouling.

Process for preparing polymers

The novel amine-functionalized polymers disclosed herein are achieved by the catalytic synthesis currently developed and disclosed using hydroaminoalkylation and Ring Opening Metathesis Polymerization (ROMP) employing Grubbs second generation catalyst ("G2"). The preparation method can convert the commercial starting materials into a variety of novel polymers without using additives or positioning groups/protecting groups, thereby minimizing the generation of wastes. A series of cyclooctene derivatives containing secondary aromatic amines are developed for atomic economy and gram scale preparation. The preparation of such amine-functionalized polyethylene analogues comprises two steps and optionally three steps. First, monomers are synthesized by catalytic hydroaminoalkylation of cycloolefins, such as cyclooctadiene, to afford an ammoalkylation of olefins in an atomically economical manner. This approach avoids amine locating or protecting groups (see FIG. 2). Next, these amine-containing monomers are then polymerized using ROMP to provide linear poly (cyclooctene) s having secondary amine side groups (see fig. 3). Third and optionally, subsequent hydrogenation reduction of the olefin then provides an amine-functionalized polyethylene, wherein each eight carbons contains a secondary amine functionality.

Aspects of the invention relate to a process for the preparation of a polyalkane of formula 5 as defined above, a process for the preparation of an amine-functional compound as defined above, a process for the preparation of a polyolefin or a polyalkane as defined above or a process for the preparation of a polymer comprising an oligomer of formula 3, formula 4 and formula 7 as defined above. These methods include: (i) Contacting a cyclic olefin with a secondary amine-containing moiety in the presence of a catalytic complex based on a group 5 metal to give a hydroaminoalkyl-substituted cyclic olefin; (ii) Ring opening metathesis polymerization of the hydroaminoalkyl-substituted cyclic olefin to obtain an amine-functionalized polyalkane; and optionally (iii) hydrogenating the amine-functionalized polyolefin from step (ii) to obtain an amine-functionalized polyalkyl, polyolefin, polyalkyl or polymer of formula 5, as the case may be.

Certain aspects of the invention also relate to a process for preparing an amine-functionalized cyclic olefin of formula 1, the process comprising: (i) Contacting the cyclic olefin with a secondary amine-containing moiety in the presence of a catalytic complex based on a group 5 metal to obtain a hydroaminoalkyl-substituted cyclic olefin.

In various embodiments, in the above methods, the secondary amine-containing moiety comprises at least two α -sp ³ A hybridized C-H bond. At each ofIn one embodiment, the secondary amine-containing moiety is C ₄ -C ₁₀₀ Linear, branched or cyclic alkyl groups optionally substituted and/or containing heteroatoms. In various embodiments, the secondary amine-containing moiety is substituted with halogen, an ester, another amine, an alkyl, an alkene, an acetal, a phosphine, an amide, an alkyne, an imine, a nitrile, an isonitrile, an epoxide, a borate; optionally substituted phenyl and/or a part of a condensed ring system, or any combination thereof. In various embodiments, the secondary amine-containing moiety is: pyrrolidine; piperidine; wherein Z is H, OCF ₃ F, cl, br, I or OCH ₃ . In various embodiments, the secondary amine-containing moiety is:

cycloolefins

In various embodiments, in the above methods, the cyclic olefin contacted with the secondary amine-containing moiety is cyclooctadiene. However, those skilled in the art will appreciate that other cyclic olefins may be used in the context of the present invention.

Catalyst complex

In various embodiments, in the above-described methods, the group 5 metal-based catalytic complex has the structure of formula I:

wherein:

R ⁵ and R is ⁶ ：

Each independently is: h is formed; c with or without substituents ₁ -C ₄₀ Linear, branched or cyclic alkyl or alkenyl or alkynyl; aryl groups with or without substituents; or a heterocyclic group having a substituent or not; or alternatively

Are bonded to each other to form a heterocyclic ring together with the nitrogen atom to which they are bonded;

R ⁷ ：

is H; c with or without substituents ₁ -C ₄₀ Linear, branched or cyclic alkyl or alkenyl or alkynyl; or aryl with or without substituents; or a heterocyclic group having a substituent or not; or alternatively

And R is R ⁵ And/or R ⁶ Bonded to form a heterocycle.

M is a group 5 metal;

a=0 to 4 and b=0 to 4, wherein the sum of a and b is 4;

each X is a halogen substituent;

each R ⁸ Independently is: h is formed; or C with or without substituents ₁ -C ₂₀ A linear, branched or cyclic alkyl group optionally containing heteroatoms. In various embodiments, each X is independently Cl or Br. In various embodiments, a=1 or a=2.

In various embodiments, R ⁵ And R is ⁶ Each independently is: a methyl group; an ethyl group; an isopropyl group; a cyclohexyl group; a phenyl group; 2, 6-dimethylphenyl; 2,4, 6-trimethylphenyl; 4-methylphenyl; piperidine optionally having a substituent; pyrrolidine optionally having a substituent; or morpholine with substituent.

In various embodiments, R ⁵ And R is ⁶ Are bonded to each other to form, together with the nitrogen atom to which they are bonded, an optionally substituted 6-membered ring.

In various embodiments: r is R ⁵ And R is ⁶ Each is phenyl; r is R ⁵ Is phenyl and R ⁶ Is isopropyl; r is R ⁵ And R is ⁶ Are bonded to each other to form, together with the nitrogen atom to which they are bonded, a piperidinyl group; r is R ⁵ Is phenyl and R ⁶ Is methyl; r is R ⁵ Is methyl and R ⁶ 1-phenethyl; r is R ⁵ Is methyl and R ⁶ Is isopropyl; or R is ⁵ Is phenyl and R ⁶ Is diphenylmethyl.

In various embodiments, R ⁷ The method comprises the following steps: a phenyl group; 2, 6-dimethylphenyl; 2, 6-di (isopropyl) phenyl; or (b)

In various embodiments, R ⁷ And R is R ⁵ And/or R ⁶ Are bonded to each other to form, together with the nitrogen atom to which they are bonded, a 5-membered ring which may be substituted. R is R ⁷ And R is R ⁵ And/or R ⁶ And each nitrogen atom to which they are bound are bonded together to form:

/>

in various embodiments, R ⁸ is-CH ₃ 、-NMe ₂ 、-CH ₂ C(CH ₃ ) ₃ or-CH ₂ Si(CH ₃ ) ₃ 。

In various embodiments, M is tantalum (Ta), niobium (Nb), or vanadium (V).

In various embodiments, in the above methods, the group 5 metal-based catalytic complex has the structure of formula II

Wherein:

R ⁵ and R is ⁶ ：

Each independently is: a methyl group; an ethyl group; an isopropyl group; a cyclohexyl group; a phenyl group; 2, 6-dimethylphenyl; 2,4, 6-trimethylphenyl; 4-methylphenyl; piperidine optionally having a substituent; pyrrolidine optionally having a substituent; or morpholine with substituent; or alternatively

Are bonded to each other so as to form, together with the nitrogen atom to which they are bonded, a 6-membered ring optionally having a substituent;

R ⁷ ：

is phenyl; 2, 6-dimethylphenyl; or 2, 6-di (isopropyl) phenyl; or alternatively

And R is R ⁵ And/or R ⁶ Are bonded to each other so as to form, together with the nitrogen atom to which they are bonded, a 5-membered ring optionally having a substituent;

each X is independently Cl or Br;

a=1 or 2 and b= (4-a); and

R ⁸ is-CH ₃ 、-NMe ₂ 、-CH ₂ C(CH ₃ ) ₃ or-CH ₂ Si(CH ₃ ) ₃ 。

In various embodiments, the group 5 metal-based catalytic complex is:

or (b)

Chlorotris (dimethylamido) (kappa) ² -N, O-3-methyl-2-pyridine) tantalum (V).

The reaction conditions may include a reaction temperature of 50 ℃ to 200 ℃, a reaction temperature of 75 ℃ to 165 ℃, a reaction temperature of 90 ℃ to 150 ℃, a reaction temperature of 110 ℃ to 130 ℃, a reaction temperature of about 110 ℃, or a reaction temperature of about 130 ℃.

The reaction conditions may include a solvent. The solvent may be aprotic. The solvent may be toluene, benzene or mixtures thereof.

The secondary amine-containing moiety and the cyclic olefin may be provided in a stoichiometric ratio of 0.1 to 1.5. The secondary amine-containing moiety and the cyclic olefin may be provided in a stoichiometric ratio of about 1:1.

Examples

Various alternative implementations and embodiments are described herein. These embodiments and examples are illustrative and should not be construed as limiting the scope of the invention. In particular, while tantalum is used as a representative group 5 metal for these studies, one skilled in the art would expect that other group 5 metals, particularly niobium, would also exhibit similar properties.

Materials and methods

The steps described herein are presented for purposes of illustration and description only and should not be taken as limiting the spirit or scope of the present invention.

1. General rule

All reactions were carried out under an inert atmosphere using a reaction vessel equipped with N ₂ And high vacuum (10) ^-3 mbar) Schlenk double manifold or full of N ₂ Is a glove box. All glassware used was heated in an oven to over 160 ℃ prior to use. The reaction was performed in a 20mL screw-threaded scintillation vial equipped with a teflon coated magnetic stirrer and a teflon lined polypropylene screw cap. Toluene and hexane were purified by passing through an activated alumina column, and then collected and stored in a glove box. Thin Layer Chromatography (TLC) was performed on EMD silica gel 60F254 plates and observed under 254nm uv light. Flash chromatography was performed using an automated biological sample purification system using SilicaFlash F60 silica gel (230 to 400 mesh) (Silicazole) as the stationary phase and ACS grade hexane/ethyl acetate as the mobile phase.

2. Reagent(s)

All reagents were purchased from commercial sources. 3-methyl-2-pyridone (Combi-blocks) are purified by sublimation. Cyclooctadiene (Aldrich), N-methylaniline (Aldrich), 4-fluoro-N-methylaniline (Aldrich) and 4-bromo-N-methylaniline (Oakwood) were mixed in CaH ₂ Stirred on for at least 2 hours, separated by distillation and then worked up using standard Schlenk techniques. 4-methoxy-N-methylaniline was prepared according to the literature and purified by sublimation. [ TaCl ] ₂ (NMe ₂ ) ₃ ]And chlorotris (dimethylamido) (kappa) ² -N, O-3-methyl-2-pyridine) tantalum (V) is prepared according to literature precedents. Purchasing and using Grubbs Catalyst ^TM Second generation (Sigma-Aldrich) without further purification.

3. Instrument for measuring and controlling the intensity of light

NMR spectra: recording at 293K ambient temperature on Bruker 300MHz or 400MHz Avance spectrometer ¹ H NMR spectrum. Record on a Bruker-Avance-300 instrument at 293K ¹³ C and C ¹⁹ F NMR spectrum. Chemical shifts (δ) are reported in parts per million (ppm). Coupling constant J is given in hertz (Hz). The following abbreviations are used to represent signal multiplexing: s = single peak; d = bimodal; dd = double doublet; t = triplet; q = quartet; m = multiple peaks; br = wide; appt=apparent. Using 1D% ¹ H、 ¹³ C{ ¹ H) and 2D (COSY, HSQC, and HMBC) NMR experiments.

Infrared (IR) spectrum: spectra were recorded at room temperature on a Perkin-Elmer-FTIR equipped with ATR accessories for direct measurement of oil and polymer materials. Wavebands in wavenumbers (cm) ^-1 ) Reported and ascribed the abbreviations s = strong, m = medium, w = weak, sh = acromion, br = broad.

Gel permeation chromatography: polymer Mn, mw and dispersibilityObtained by triple detection Gel Permeation Chromatography (GPC) using a Waters liquid chromatograph equipped with an Agilent 1200 series isocratic pump and autosampler, a Phenomenex Phenomenex μm narrow-well column, a Wyatt optilareex differential refractometer, wyatt tristar miniDAWN (laser scattering detector) and a Wyatt ViscoStar viscometer. A flow rate of 0.5 ml.min-1 was used and the sample was dissolved in THF (about 2 mg.ml ^-1 ) Is a kind of medium. The measurement was performed at a laser wavelength of 690nm at 25 ℃. Use Wyatt Technology Corp to provide->The handler analyzes the data.

Differential Scanning Calorimetry (DSC): DSC was completed on TA Instruments DSC Q2000 equipped with TA Instruments Refrigerated Cooling System 90. In the range of-90 ℃ to 120 ℃, a heating/cooling rate of 5 ℃/min was used per run. The measurement is run repeatedly after one heating/cooling cycle is completed to eliminate the thermal history.

Thermogravimetric analysis (TGA): a Shimadzu TGA-60 thermogravimetric analyzer was used to perform TG measurements on the samples. Small amounts (3 to 5 mg) were analyzed using an alumina crucible. The sample was preheated in a TGA oven at 105 ℃ for 15 minutes to remove moisture. The samples were then tested at a rate of 10 ℃/min under a nitrogen atmosphere at 30 ℃ to 600 ℃.

Rheological measurements: rheological characterization was performed using an Anton Paar MCR 702 rotational rheometer equipped with a conical baffle geometry. The main advantage of this geometry is the elimination of edge breaks ²⁹ . The top of this geometry includes a 8mm diameter plate (center plate) attached to the sensor, and a coaxial retaining ring (spacer, 25mm diameter) that acts as a shield and prevents the sample edge from breaking. The diameter of the bottom plate is 25mm and the angle is 0.07rad. The test was performed with a distance gap of 51 μm.

The thermal stability of the samples was monitored isothermally for 2 hours using a frequency of 0.1Hz and a shear strain of 0.01. The threshold value of the linear viscoelastic region was determined by an initial strain sweep test at a frequency of 0.1 Hz. Frequency sweep experiments (0.01 to 100 Hz) were performed at different temperatures with a fixed shear strain of 0.01, which allowed the use of the time-temperature superposition principle (tTS) and the generation of a total curve for each sample at the reference temperature. Experiments were performed in triplicate and representative data was provided.

4. Synthesis and results

Synthesis of group V metal catalyst complexes (including chlorotris (dimethylamido) (kappa) useful in the context of the invention ² The general method of-N, O-3-methyl-2-pyridine) tantalum (V)) is described in International patent application PCT/CA2018/050619, publication No. WO 2018/213938, the contents of which are incorporated herein by reference.

4.1 Chlorotris (dimethylamido) (kappa) ² -N, O-3-methyl-2-pyridine) tantalum (V)

At room temperature, to [ TaCl ] ₂ (NMe ₂ ) ₃ ] ₂ (0.23 g,0.3 mmol) to a suspension of sodium 3-methyl-2-pyridinate (0.075 g,0.6 mmol) in toluene (about 2 mL) was added. After stirring overnight, the initially yellow, cloudy mixture turned into an orange, clear solution. Volatiles were removed in vacuo to give 0.250g of an orange-brown oil (90%). The crude residue was dissolved in 1.0g toluene solvent (0.25 wt./wt.%) and used for Hydroaminoalkylation (HAA). ¹ H NMR(400MHz，d ₈ -tol)：δ8.23(d of d,1H,ArH),δ6.83(d,1H,ArH),δ6.20(t,1H,ArH),δ3.75-3.53(br s,18H,(NCH ₃ ) ₂ ) ₃ )δ2.10(s,3H,CH ₃ ). The characterization is consistent with the previously reported values.

4.2 hydroaminoalkylation:

FIG. 2 depicts a general scheme for hydroaminoalkylation of cycloalkenes in accordance with the present invention. Use of catalyst chlorotris (dimethylamido) (kappa) ² -N, O-3-methyl-2-pyridinic acid) tantalum (V), the hydroaminoalkylated monomer derived from cyclooctadiene being prepared by a hydroaminoalkylation reaction. Although for simplicity, only chlorotris (dimethylamido) (κ) is used in the embodiments illustrated herein ² -N, O-3-methyl-2-pyridinic acid) tantalum (V), but the skilled person will appreciate that other group 5 metal based catalytic complexes as described herein may be used to produce the amine functionalized cyclic olefins and polymers disclosed herein. Similarly, the skilled artisan will appreciate that while only cyclooctadiene is used in the embodiments illustrated herein, additional cyclic olefins may be used to produce the amine-functionalized cyclic olefins and polymers disclosed herein. All reported yields were calculated after column chromatography.

Referring to fig. 2, the catalyst complex exhibited yield and multi-gram scale reactivity (see fig. 2). Using this catalytic system, 4 different amine-functional monomers (M1-M4) were obtained with a variety of para-substituted N-methylanilines, including halide and methoxy-functional aniline substituents. By using a small excess of cyclooctadiene (1.5 equivalents), only a small amount of the dialkylated product is formed as a secondary byproduct (< 15%) and then removed by column chromatography to give the desired aminated cyclooctene monomer in high yields (> 81%).

(Z) -N- (cycloocta-4-en-1-ylmethyl) aniline (amine-functionalized cyclic olefin "M1"): to chlorotris (dimethylamido) (kappa) ² To a solution of tantalum (V) (200 mg,5 mol%) N-methylaniline (1 g,9.34 mmol) in toluene (ca. 3 mL) was added followed by cyclooctadiene (1.54 g,14 mmol). The initial orange cloudy solution was fitted with a stirrer, capped, taken out of the glove box and heated to 145 ℃ in an oil bath. After reaching temperature, the reaction mixture became dark red and was then heated with stirring for 20 hours. After this time, the reaction was exposed to ambient air and quenched by the addition of about 1mL of methanol. Purification was accomplished by automatic column chromatography (0 to 20% ethyl acetate/hexanes gradient) to give 1.68g of a pale yellow oil (84.0%). ¹ H NMR(300MHz，CDCl ₃ Fig. 7 a): delta 7.20 (d of d, ³ J _AB ＝7.35Hz, ³ J _AC ＝8.53Hz,2H,2×ArH),δ6.72(t, ³ J _AB ＝7.39Hz,1H,ArH),δ6.64(d, ³ J _AC ＝8.79Hz,2H,2x ArH),δ5.68(m,2H,2x RHC＝CHR),δ4.09(br s,1H,NH),δ2.96(m,2H,CH ₂ ),δ2.38(m,1H,CH),δ2.16(m,3H,CH ₂ ),δ1.81-1.19(m,7H,CH ₂ )。 ¹³ C{1H}NMR(75MHz，CDCl ₃ fig. 7 b): delta 148.7 (C), delta 130.2 (CH), delta 130.1 (CH), delta 129.3 (CH), delta 117.0 (CH), delta 112.7 (CH), delta 51.7 (CH) ₂ ),δ37.8(CH ₂ ),δ33.5(CH ₂ ),δ31.2(CH ₂ ) Delta 28.3 (CH), delta 26.0 (CH), delta 24.9 (CH) IR (pure oil, cm) ^-1 Int): 3428br,3019w,2924s,2856sh,1600s,1506s,1314m,1252w,1125br,994br,749s,689s HRMS-ESI (m/z) calculated: 216.1752; experimental values: 216.748.

(Z) -N- (cyclooct-4-en-1-ylmethyl) -4-fluoroaniline (amine functionalized cyclic olefin "M2"): prepared according to M1 using 4-fluoro-N-methylaniline as the amine substrate provided 1.53g of a pale yellow oil (81.7%). ¹ H NMR(300MHz，CDCl ₃ Fig. 8 a): delta 6.90 (t, 2H,2 XArH), delta 6.72 (m, 2H,2 XArH), delta 5.69%m,2H,2x RHC＝CHR),δ3.50(br s,1H,NH),δ2.91(m,2H,CH ₂ ),δ2.38(m,1H,CH),δ2.17(m,3H,CH ₂ ),δ1.79-1.19(m,7H,CH ₂ )。 ¹³ C{1H}NMR(75MHz，CDCl ₃ Fig. 8 b): delta 157.2 (C), delta 154.1 (CH), delta 145.0 (CH), delta 130.1 (CH), delta 115.4 (CH), delta 113.5 (CH), delta 52.4 (CH) ₂ ),δ37.7(CH ₂ ),δ33.4(CH ₂ ),δ31.2(CH ₂ ),δ28.2(CH),δ25.9(CH),δ24.8(CH)。 ¹⁹ F{1H}NMR(282MHz，CDCl ₃ Fig. 8 c): delta-128.6 IR (pure oil, cm) ^-1 Int): 3428br,3010w,2909m,2856sh,1615w,1513s,1470sh,1320w,1221s,814s,720m HRMS-EI (m/z) calculated: 233.15798; experimental values: 233.15817.

(Z) -N- (cycloocta-4-en-1-ylmethyl) -4-bromoaniline (amine-functionalized cycloolefin "M3"): prepared according to M1 using 4-bromo-N-methylaniline as the amine substrate, providing 1.29g of a pale yellow oil (81.3%). ¹ H NMR(300MHz，CDCl ₃ Fig. 9 a): delta 7.25 (d, ³ J _AB ＝8.77Hz,2H,2×ArH),δ6.48(d, ³ J _AB ＝8.77Hz,2H,2x ArH),δ5.68(m,2H,2x RHC＝CHR),δ3.78(br s,1H,NH),δ2.91(m,2H,CH ₂ ),δ2.36(m,1H,CH),δ2.17(m,3H,CH ₂ ),δ1.78-1.18(m,7H,CH ₂ ) ¹³ C{1H}NMR(75MHz，CDCl ₃ fig. 9 b): delta 147.5 (C), delta 131.9 (CH), delta 130.1 (CH), delta 114.3 (CH), delta 108.5 (CH), delta 51.7 (CH) ₂ ),δ37.6(CH ₂ ),δ33.4(CH ₂ ),δ31.1(CH ₂ ) Delta 28.2 (CH), delta 26.0 (CH), delta 24.8 (CH)) IR (pure oil, cm) ^-1 Int): 3422br,3015w,2922s,2854sh,1593s,1497s,1313m,1249m,1175w,1073w,999w,808s,723m HRMS-ESI (m/z) calculated: 293.07791; experimental values: 293.07770.

(Z) -N- (cycloocta-4-en-1-ylmethyl) -4-methoxyaniline (amine-functionalized cycloolefin "M4"): prepared according to M1, using 4-methoxy-N-methylaniline as the amine substrate, provided 1.52g of yellow oil (85.0%). ¹ H NMR(300MHz，CDCl ₃ Fig. 10 a): delta 6.81 (d, ³ J _AB ＝9.24Hz,2H,2×ArH),δ6.60(d, ³ J _AB ＝8.79Hz,2H,2x ArH),δ5.68(m,2H,2x RHC＝CHR),δ3.77(s,3H,OCH ₃ ),δ3.38(br s,1H,NH),δ2.91(m,2H,CH ₂ ),δ2.38(m,1H,CH),δ2.18(m,3H,CH ₂ ),δ1.81-1.19(m,7H,CH ₂ ) ¹³ C{1H}NMR(75MHz，CDCl ₃ fig. 10 b): delta 152.0 (C), delta 142.7 (CH), delta 130.2 (CH), delta 115.0 (CH), delta 114.1 (CH), delta 55.9 (CH) ₃ ),52.9(CH ₂ )δ37.7(CH ₂ ),δ33.5(CH ₂ ),δ31.2(CH ₂ ) Delta 28.2 (CH), delta 26.0 (CH), delta 24.9 (CH). IR (pure oil, cm) ^-1 ): 3415br,3014w,2919s,2854sh,1620w,1506s,1463m,1228s,1125w,1035m,818s,724w HRMS-EI (m/z) calculated: 245.17796; experimental values: 245.17794.

(Z) -N- (cycloocta-4-en-1-ylmethyl) -4- (methylthio) aniline (amine-functionalized cycloolefin "M5"): prepared according to M1 using N-methyl-4- (methylthio) aniline (2.5 g) as the amine substrate, provided 1.52g of a yellow oil (71%). ¹ H NMR(300MHz，CDCl ₃ )：δ7.22(d of d, ³ J＝8.7Hz, ³ J＝2.5Hz,2H,2×ArH),δ6.54(t, ³ J＝8.7Hz,1H,ArH),δ5.67(m,2H,2x RHC＝CHR),δ3.88(br s,1H,NH),δ2.93(m,2H,CH ₂ ),δ2.42(s,3H,CH ₃ ),δ2.38(m,1H,CH),δ2.16(m,3H),δ1.77-1.19(m,7H) ¹³ C{1H}NMR(75MHz，CDCl ₃ )：δ146.9(C),δ131.5(CH),δ130.1(CH),δ124.2(C),δ113.6(CH),δ51.9(CH ₂ ),δ37.5(CH ₂ ),δ33.3(CH ₂ ),δ31.1(CH ₂ ),δ28.1(CH),δ25.9(CH),δ24.7(CH),δ19.2(CH ₃ ). IR (pure oil, cm) ^-1 Int): 3417br,3013w,2915vs,2850s,1598vs,1500vs,1466m,1437w,1400w,1367w,1312m,1289m,1248m,1201w,1181w,1128w,1103w,966w,884w,812m,756w,722m HRMS-ESI (m/z) calculated: 262.1629; experimental values: 262.1637.

(Z) -N- (cyclooct-4-en-1-ylmethyl) -cyclohexylamine (amine-functionalized cyclic olefin "M6"): prepared according to M1, using N-methylcyclohexylamine (0.45 g) as the amine substrate, to provide 0.6g of a yellow oil (53%). ¹ H NMR(300MHz，CDCl ₃ )：δ5.64(m,2H,2x RHC＝CHR),δ2.44(m,3H,N-CH ₂ ,N-CH),δ2.34(m,1H,CH),δ2.12(m,3H),δ1.88-1.00(m,18H) ¹³ C{1H}NMR(75MHz，CDCl ₃ )：δ130.2(CH),δ129.9(CH),δ56.9(CH),δ54.9(CH ₂ ),δ38.1(CH),δ33.7(CH ₂ ),δ33.6(CH ₂ ),δ31.6(CH ₂ ),δ28.2(CH),δ26.2(CH ₂ ),δ25.9(CH ₂ ),δ25.1(CH ₂ ),δ24.9(CH ₂ ). IR (pure oil, cm) ^-1 Int): 3014w,2923vs,2851s,1651m,1612w,1570w,1463s,1449s,1374w,1348w,1258w,1228w,1131m,1028w,989w,972w,941w,886m,844w,775m,754m,721vs HRMS-ESI (m/z) calculated: 222.2222; experimental values: 222.2228.

table 1 provides an overview of synthetic exemplary amine-functionalized cyclic olefins.

TABLE 1 overview of synthetic amine-functionalized cycloolefins

Using Grubbs Catalyst generation 2, these monomers with side chain secondary aromatic amines are subject to ROMP to obtain linear polymers.

4.3 polymerization

FIG. 3 depicts a general scheme for polymerization of hydroaminoalkylated cycloolefin monomers according to the present invention. Using Grubbs Catalyst ^TM The polymerization of the amine-functionalized cycloolefin monomers M1, M2, M3 and M4 is accomplished by Ring Opening Metathesis Polymerization (ROMP) at generation 2. Typically, the catalyst is stirred over CH ₂ Cl ₂ Is added to the solution of the monomer in CH ₂ Cl ₂ Is in solution in the reactor. The reaction is carried out at room temperature in gram-scale quantities to obtain high conversion of the monomers. The reaction was allowed to proceed for at least 1 hour to ensure complete conversion. After the reaction was completed, the solution was slowly changed from the original dark amber solution to light amber-yellow/green. By exposure to ambient air and dropwise addition of excess ethyl vinyl ether (per mg [ Ru ] ]At least 2 drops of catalyst) to terminate the reaction and remain stirred for at least 30 minutes after which the solution slowly turns dark amber/black in color. By dropping into a stirring methanol vortex (-35 ℃ and at least 1mL per mg of polymer), the polymer precipitated as a colloidal off-white solid with a physical appearance that was significantly different from the non-functionalized poly (cyclooctene) precipitated as a white flocculent solid. Separation was accomplished by decanting the supernatant and drying the collected material overnight under high vacuum. SubsequentlyAll characterization was done except GPC analysis, for which the polymer was purified by two additional precipitations (CH ₂ Cl ₂ The solution was added to a large excess of methanol) and then dried in a vacuum oven to complete further purification.

Poly (N- (cycloocta-4-en-1-ylmethyl) aniline) (polymer "P1"): prepared as above to provide 0.602g of an off-white gummy solid (81%). ¹ H NMR(300MHz，CDCl ₃ Fig. 11 a): delta 7.17 (m, 2h,2×arh), delta 6.73 (br s,3h,3×arh), delta 5.40 (m, 2h,2×rhc=chr), delta 3.03 (d, 2h, ch) ₂ ),δ2.00(m,4H,CH ₂ ),δ1.68(br s,1H,CH),δ1.49-1.26(m,6H,CH ₂ ) IR (absolute, cm) ^-1 Int, fig. 11 b): 3425br,2924s,2847sh, 292 s,1505s,1430sh,1320m,1258m,1180w,1023w,964m, 8622 w,743s,691s.

Poly (N- (cycloocta-4-en-1-ylmethyl) -4-fluoroaniline) (polymer "P2"): prepared as above to provide 0.690g of a gummy off-white solid (88%). ¹ H NMR(300MHz，CDCl ₃ Fig. 12 a): delta 6.87 (m, 2h,2×arh), delta 6.55 (br s,2h,2×arh), delta 5.39 (m, 2h,2×rhc=chr), delta 2.97 (d, 2h, ch) ₂ ),δ2.00(m,4H,CH ₂ ),δ1.63(br s,1H,CH),δ1.36(br s,6H,CH ₂ ) ¹⁹ F{1H}NMR(282MHz，CDCl ₃ ): delta-127.7 IR (absolute, cm) ^-1 Int, fig. 12 b): 3419br,2919m,2850sh,1614w, 660 s,1473sh,1316w,1214s,1101w,816s

Poly (N- (cycloocta-4-en-1-ylmethyl) -4-bromoaniline) (polymer "P3"): prepared as above to provide 0.592g of a gummy off-white solid (94%). ¹ H NMR(400MHz，CDCl ₃ Fig. 13 a): delta 7.27 (m, 2h,2×arh), delta 6.52 (br s,2h,2×arh), delta 5.42 (m, 2h,2×rhc=chr), delta 3.00 (d, 2h, ch) ₂ ),δ2.01(br s,4H,CH ₂ ),δ1.66(br s,1H,CH ₂ ),δ1.38(br s,6H,CH ₂ ) IR (absolute, cm) ^-1 Int, fig. 13 b): 3422br,2922s,2854sh,1593s,1497s,1313m,1249m,1175m,1073m,964m, 178 s.

Poly (N- (cycloocta-4-en-1-ylmethyl) -4-methoxyaniline) (polymer "P4"): prepared as above to provide 0.541g of a gummy off-white solid (88%). ¹ H NMR(400MHz，CDCl ₃ FIG. 14a)：δ6.78(d,2H,2×ArH),δ6.59(br s,2H,2x ArH),δ5.39(m,2H,2x RHC＝CHR),δ3.74(s,3H,OCH ₃ ),δ2.98(d,2H,CH ₂ ),δ2.01(br s,4H,CH ₂ ),δ1.63(br s,1H,CH ₂ ),δ1.37(br s,6H,CH ₂ ) IR (absolute, cm) ^-1 Int, fig. 14 b): 3394br,2923s,2848sh,1655br, 660 s,1464sh,1233s,1017s,816s,668m.

Poly (N- (oct-4-en-1-ylmethyl) -4- (methylthio) aniline (polymer "P5"): was prepared as above to provide a dark purple solid (70%). ¹ H NMR(300MHz，CDCl ₃ )：δ7.22(m,2H,2×ArH),δ6.54(m,2H,2×ArH),δ5.40(br s,2H,2x RHC＝CHR),δ3.69(br s,1H,NH),δ2.99(m,2H,CH ₂ ),δ2.42(m,3H,CH ₃ ) Delta 1.99 (m, 4H), delta 1.77-1.19 (m, 7H) IR (absolute, cm) ^-1 ，int)：3414br,2917s,2852m,1597vs,1500vs,1474m,1455m,1435w,1401w,1312m,1289m,1250m,1181m,1101w,966s,812s,735w。

Poly (N- (oct-4-en-1-ylmethyl) -cyclohexylamine (polymer "P6"): prepared as above to provide a dark orange solid (42%). ¹ H NMR(300MHz，C ₇ D ₈ )：δ5.53(br s,2H,2x RHC＝CHR),δ2.55(br s,2H,CH ₂ ),δ2.37(m,1H,CH),δ2.11(br s,4H,CH ₂ ),δ1.86-1.07(m,17H,CH,CH ₂ ) Delta 0.52 (br s,1H, NH) IR (absolute, cm ^-1 ，int)：2921vs,2851s,1670w,1449s,1365w,1347w,1259w,1241w,1130m,966vs,922w,888m,845m,845w,786w,723s。

Polymers P1 to P6 are produced in high yields regardless of the secondary amine substituent pendant groups>80%) was obtained. ¹ Chemical shift analysis of the H NMR spectrum indicated that signal broadening was consistent with polymer formation. For example, for polymer P2, in ¹⁹ A main peak was observed in the F NMR spectrum; delta-127.7 ppm has a broad single peak, whereas for Polymer P4 the methoxy substituent provides a characteristic NMR signal at ¹ It was observed in the H NMR spectrum to be a broad single peak (. Delta.3.74 ppm); furthermore, the peak integral was a 3:2 ratio compared to olefin resonance at δ5.41 ppm. In the case of M1, the crude reaction mixture of the hydroaminoalkylation is readily subjected to the ROMP reaction without column chromatography purification, but the resulting materials, such as P2 and P4, are only accessible to NMR and IR lightThe spectra were characterized.

Table 2 provides an overview of synthetic exemplary polymers.

TABLE 2 overview of synthetic polymers

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4.4 hydrogenation

The hydrogenation reduction of the polymer backbone of the polymer P1 was targeted to obtain a saturated polymer like polyethylene. Reduction can be achieved using tosyl hydrazide of c=c double bond of the selectively reduced polymer P1 as hydrogen source. Because of the presence of secondary amine side groups, substantial post-treatment of the polymer is required.

Poly (N- (cycloocta-4-en-1-ylmethyl) aniline) (polymer "PH 1"): p1 (480 mg,2mmol of olefin) and P-toluenesulfonyl hydrazine (1.5 g,8 mmol) in xylene (15 mL) were added together with a small amount of 2,4, 6-tri-tert-butylphenol added as a free radical sponge to a 100mL reaction vessel equipped with a Teflon top valve and side arms and a Teflon coated stirrer. Charging the obtained heterogeneous mixture with N ₂ Thawing with a cryopump three times, and then refilling with N ₂ . The vessel was sealed and heated to 130 ℃ in an oil bath for at least 8 hours. After the duration of the reaction, a pale yellow transparent solution was obtained. The vessel was opened and the mixture was transferred to a separatory funnel and quantitatively transferred with ethyl acetate (50 mL). The organic layer was washed three times with 3M NaOH, then once with brine, then reduced to about 3mL by rotary evaporation under reduced pressure. The residue was then added dropwise to a large excess of methanol vortex (-35 ℃,250 mL), thereby providing an off-white gummy solid product. After three excessive precipitations, 0.350g of material (73.0%) was obtained. ¹ H NMR(300MHz，CDCl ₃ Fig. 15 a): delta 7.17 (m, 2H,2 XArH), delta 6.69 (t, 1H, arH), delta 6.63 (d, 2H, arH), delta 3.01 (d, 2H, CH) ₂ ),δ1.61(br s,1H,CH),δ1.28(m,14H,CH ₂ ) IR (absolute, cm) ^-1 Int, fig. 15 b): 3420br,3045w,2922s,2849sh,1601s, 1500 s,1466sh,1316m,1261m,1095br,1030br, 254 s,746s,689s.

Table 3 provides an overview of synthetic exemplary hydrogenated polymers.

TABLE 3 overview of exemplary Compounds

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Secondary aromatic amines and their substituents can be altered to modulate hydrogen bond interactions, which can result in polymers exhibiting different physical properties, such as liquid, gel-like, soft, or solid structures.

Example 2: NMR polymerization study

Polymerization of M1 was monitored by NMR spectroscopy. Grubbs initiator, 100 equivalents of M1 and about 1 ml of deuterated chloroform were added to the sealed NMR tube. After 10 minutes, about 35% of the monomer was consumed; after 30 minutes, the reaction was more than 95% complete. The rapid conversion of M1 compared to other amine functional monomers (incompatible with Grubbs initiator) indicates that aryl substituted secondary amines are susceptible to ROMP reactions. Notably, the signal ascribed to the benzylidene ru=chph proton at 19.2ppm was still present in the spectrum throughout the polymerization (fig. X), where this observation may indicate incomplete initiation of the catalyst, and a propagation rate greater than the initiation rate of the catalyst.

To investigate whether chain termination occurred at the completion of the reaction, an aliquot of about 25 equivalents of M2 was added long after complete consumption of monomer M1 (12 hours). After the addition of M2, a rapid polymerization reaction occurred, after 30 minutes no signal was observed consistent with the internal olefins of M2, while the overlapping olefin peaks of P1 and P2 indicated that the polymerization was not self-terminating, requiring the addition of a quencher to complete the reaction. In addition, in the case of the optical fiber, ¹⁹ F NMR spectra showed a single broad singlet state, consistent with the open-loop M2 polymer material, confirming ¹ Evidence exists in H NMR spectra.

4.4 molecular weight and dispersity

Polymers having solubility in Tetrahydrofuran (THF) were analyzed by Gel Permeation Chromatography (GPC) to investigate the molecular weight and dispersity of the polymers (table 2). Experimental molecular weight to monomer-initiator ratio (M _n,theo ＝[M]/[I]) Is not completely correlated, and a dispersity of 1.1 to 1.6The values indicate that the polymerization is only carried out with moderate control. As previously mentioned, reaction monitoring shows a faster rate of increase relative to initiation, resulting in a greater molecular weight than expected and an increase in polymer dispersion. Notably, for GPC analysis, not all isolated polymers have solubility in THF; for example, P4 containing a hydrogen-bonded methoxy substituent can be characterized by NMR in chloroform but is not completely soluble in THF or chloroform. This observation suggests that the formation of a broad network of hydrogen bonds may lead to a decrease in the solubility of the polymer due to an increase in intermolecular and intramolecular forces. P2 also shows this insufficient solubility, probably due to the strong H-bond bonding potential of the fluoro substituent.

TABLE 2 Experimental and theoretical molecular weights (M _n )

^a Gel Permeation Chromatography (GPC) measurement

4.5 thermal stability

The thermal stability (weight loss) of the polymer was determined using dynamic TGA experiments. Each sample was preheated at 105 ℃ for 5 minutes and then heated from 30 ℃ to 600 ℃ under nitrogen and oxygen at a heating rate of 10 ℃/minute.

The three measurements were averaged. The TGA profile of the test samples was not different under nitrogen or oxygen atmosphere, indicating good thermal oxidation stability. Fig. 4a and 4b show selected weight loss curves, table 4 summarises the 5% weight loss temperature of the tested polymers. The results show that poly (cyclooctene) (P (Cyclooctene)) is a thermally stable polymer with only one weight loss step at 415 ℃, which is attributed to degradation of the polymer chain. The functionalization P1 shows a two-step weight loss. The initial weight loss at about 300 ℃ is attributed to the loss of the pendant N-methylaniline groups. The second thermal degradation at around 420 ℃ refers to degradation of the polymer backbone. In general, polymers follow a free radical degradation mechanism, which is initiated by bond dissociation at pyrolysis temperatures. By observing the structure and bond strength of the polymer, it was found that a possible initial degradation mechanism of the poly (pendant amine) (PPA) polymer might be through pendant group elimination.

The TGA or DTG derivative curves help to determine overlapping mass loss events, identify smaller mass loss steps, and find the maximum of the weight loss process, where each peak of the TG curve may be an isolated event, which may indicate the maximum mass loss rate. Referring to fig. 5, a thermal spectrum obtained by Differential Scanning Calorimetry (DSC) shows typical behavior of an amorphous polymer. The glass transition temperature is attributed to the chain transition from the glass region to the rubber region, and table 4 summarizes the glass transition temperature values for each polymer.

TABLE 4 thermal characterization by differential scanning calorimetry and thermogravimetry

Polymer	T _g (℃)	T _5％ (℃)
			Poly (cyclooctene)	-	415
P1	-13.7	275
			P2	-10.4	280
P3	-2.0	255
			P4	-4.7	287
P1H	-16.8	400

4.6 rheology

Representative overall plots of shifted storage and loss moduli and complex viscosity of various amine derivatives of poly (cyclooctene) as a function of angular frequency of offset are depicted in fig. 6 a-6 e. A number of significantly different rheological behaviour is obtained, possibly due to the different aromatic amines promoting different hydrogen bonding environments. The information obtained for P1, P1H prehydrogenation, P1H and P3 is reported in tables 5A to 5D below.

P1 shows liquid-like behaviour (G "> G'), while P3 and P4 show a transition from liquid-like behaviour through gel-like behaviour to solid-like behaviour. P2 exhibits a soft-solid-like behavior (G '. Gtoreq.G') which is made more pronounced by the introduction of polar F functional groups which may also be involved in hydrogen bonding interactions. Furthermore, the presence of strong F-H bonds may be responsible for the formation of a 3D network, resulting in the material exhibiting a viscoelastic solid with a higher melting temperature than the reference material. The transition from liquid to solid is evident when comparing the storage modulus of P1 and P2. Strong physical crosslinking of P2 was observed during the preparation/formation of the film using the solution casting method. This may be explained by the arrangement of the polymer chains in solution making hydrogen bonding easier to form. P3 and P4 exhibit significantly zero shear viscosity, higher than P3. The bromo-functionalized poly (cyclooctene) may form stronger hydrogen bond structures due to the potentially higher molecular weight.

TABLE 5 rheological behavior of Polymer P1

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TABLE 5 rheological behavior of Polymer P1H before hydrogenation

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TABLE 5 rheological behavior of Polymer P1H

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TABLE 5D rheological behavior of Polymer P3

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4.7 self-healing Properties

Referring to fig. 17, the polymers disclosed herein have self-healing properties. The self-healing properties of these polymers appear to be related to their ability to have chain mobility as amorphous materials.

4.8 copolymers

4.8.1 copolymers with cyclooctene

In an attempt to explore the extent to which the advantageous properties of these novel polymers can be maintained at lower amine incorporation levels in the polymer, the amine incorporation levels in the final polymer were reduced by adding excess cyclooctene in the ROMP reaction. The ultimate goal is to maintain the desirable properties imparted by the amine functionality while reducing its incorporation into the cheaper, less functionalized polyolefin.

Polymers with reduced amine incorporation were synthesized according to the following protocol.

The general preparation method of the copolymer with the molar ratio of P (P1-co-cyclooctene) of 1:1 is as follows: a solution of a first monomer, such as cyclooctene (51 mg,0.4 mmol), and G2 (3.7 mg, 0.04 mmol) in THF (1 mL) was added to a 20mL scintillation vial with a stirrer. After the first monomer has been reacted at room temperature for the desired time (e.g., 4 hours for cyclooctene), the second monomer, e.g., M1 (100 mg,0.4mmol; molar ratio to cyclooctene is 1:1). After the time required for the reaction of the second monomer, the entire reaction Terminated and the polymer was isolated using standard protocols by adding vinyl ether and precipitating into methanol. ¹ H NMR(300MHz，CDCl ₃ )：δ7.19(m,2H,2×ArH),δ6.71(br s,3H,3x ArH),δ5.40(m,4H,RHC＝CHR),δ3.03(d,2H,CH ₂ ),δ2.00(m,8H,CH ₂ ),δ1.68(br s,1H,CH),δ1.49-1.26(m,14H,CH ₂ ). The synthesis results are further reported in table 6 below.

TABLE 6

Molecular weight of quenched aliquots using P1, then by using ¹ Integration in the H NMR spectrum to correlate MW of P2, thereby determining M _n,calc 。

4.8.2 copolymers having aromatic amine-substituted norbornene monomer units

Polymers formed from aromatic amine substituted norbornene monomers do not exhibit self-healing behavior as compared to the polymers disclosed and prepared herein. It is interesting to combine these monomers to explore whether this behaviour can be tuned and allow the preparation of materials with variable physical properties.

The copolymers of amine-functionalized cyclic olefin monomers and several aromatic amine-substituted norbornene monomers disclosed above include:

the monomers ACN-1 and ACN-4 can be prepared as disclosed by Perry et al (Macromolecules, 49:4423-4430).

While adding monomers for attempting to form a copolymer.

Different combinations of a series of monomers with different para R/R' substituents (50 equivalents per monomer) were copolymerized by ROMP. Copolymers are prepared as homopolymers using various stoichiometric amounts of different monomers to give the theoretical ratio of polymer product. The typical procedure is as follows:

P(ACN-1-co-P2)

ACN-1 (50 mg,0.25 mmol) and Polymer P2 (58 mg,0.25 mmol) and about 1mL CH were added to a 20mL scintillation vial ₂ Cl ₂ . To this solution was added Grubbs Catalyst ^TM Generation 2 ("G2"; 4.2mg,0.005 mmol) in about 1mL CH ₂ Cl ₂ Is a solution of (a) a solution of (b). The reaction was stirred at room temperature for 20 hours during which time the solution slowly changed from the original amber to brown-green. Using standard protocols, the polymer was isolated by adding vinyl ether and precipitating into methanol; yield was quantitative, with losses caused by precipitation collection. ¹ H NMR(300MHz，CDCl ₃ )：δ7.16(s,2H,2×ArH),δ6.87(m,2H,2×ArH),δ6.75(m,3H,3ArH),δ6.55(br s,2H,2x ArH),δ5.39-5.27(m,4H,2x RHC＝CHR),δ3.05-2.97(d,4H,CH ₂ ),δ2.90(s,1H,CH),δ2.53(s,1H,CH),δ2.00-1.95(m,6H,CH ₂ ),δ1.65-1.63(br s,3H),δ1.36(br s,6H,CH ₂ ),δ1.19(s,1H,CH)。

The quenched reaction solution was separated by precipitation to give materials with physical properties intermediate to those of the homopolymers. Homopolymers made from aromatic amine substituted norbornene monomers are hard-wired, whereas when the homopolymers disclosed herein are tough viscose, the copolymers are clustered together and as tacky as the latter, but have a more pronounced stiffness. By passing through ¹ H NMR spectra, the resulting polymer was found to have a higher ACN incorporation efficiency (52% to 74%). ACN-1 (r=h) and ACC-2 (R' =f) were chosen as model systems because both monomers were homogeneously incorporated (52:48 ACN: ACC). To ensure that a copolymer is formed instead of two homopolymers, GPC analysis was performed on the sample; a peak was observed, reasonably consistent with theory (M _n,exp ＝18,130g·mol ^-1 ，M _n,theo .＝21,630g·mol ^-1 )。

To investigate whether thermal properties can be adjusted based on the relative amounts of monomers incorporated, three different ratios of polymer P (ACN-1-co-P2) model systems were prepared. From the following components ¹ The experimental ratios of the H NMR spectrum measurements are shown in table 7. The glass transition temperatures measured by DSC are shown in Table 7 and FIG. 18. As shown in fig. 18, by adjusting the feed ratio of the two monomers, the glass transition can be adjusted. The single glass transition observed in each sample also indicates the synthesis of copolymers in which the two blocks are miscible.

TABLE 7 proportions of monomers in the copolymers

The effect of different ratios on viscoelasticity was examined. Referring to FIG. 19, a melt rheology study was performed on model copolymers with equal amounts of ACN-1 and M2 segments. The P (ACN-1-co-P2) copolymer exhibits rheological properties intermediate to those of two pure homopolymers. Polymer P2 showed that the loss modulus predominated over the entire frequency range, exhibiting liquid-like behavior. The storage modulus is dominant in the soft solid material P (ACN-1). In the copolymer, the storage modulus and loss modulus are approximately equal at low frequencies; at higher frequencies, storage modulus dominates, with a crossover point at the termination region. The rheological behavior observed also indicates that the copolymer has miscible domains.

Changes in glass transition temperature (T) were investigated by qualitative healing experiments _g ) Is a function of (a) and (b). It is assumed that all samples having glass transition below room temperature will exhibit self-healing properties. Of the three copolymers, only the M2 to ACN-1 ratio was 3:1 (T _g Samples =8.6 ℃) showed healing within 24 hours. ACN-1 is 1:1 (T) _g Samples =17.3 ℃) did not show healing at ambient conditions. These results indicate that adjusting thermal behavior can adjust healing time depending on the needs of the material.

While specific embodiments of the invention have been described and illustrated, these embodiments should be considered illustrative of the invention only and not as limiting the invention as construed in accordance with the accompanying claims. Many adaptations and modifications may be made within the scope of the invention, based on common general knowledge of a person skilled in the art. Such modifications include substitutions of known equivalents to any aspect of the invention in order to achieve the same result in substantially the same way.

Claims

1. An amine-functional compound of formula 2:

wherein the method comprises the steps ofIs a single bond;

Wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

Wherein Y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is CR ¹ R ² -NR ³ R ⁴ And the rest of Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl or a substituted or unsubstituted heterocycle;

wherein R is ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group, provided that R ³ And R is ⁴ At least one of which is not H; or wherein R is ³ And R is ⁴ To form a ring portion, or wherein R ³ And R is ⁴ One of which is with R ¹ And R is ² To form a ring portion;

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n is a natural number greater than 2, and

wherein the repeat units in brackets in formula 2 are linked in a head-to-head manner, a head-to-tail manner, a tail-to-tail manner, or any combination thereof.

2. The amine-functional compound of claim 1, wherein X ¹ 、X ² 、X ³ And X ⁴ Each is H.

3. The amine-functional compound of claim 1, wherein X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ 。

4. The amine-functional compound of claim 1, wherein X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ 。

5. The amine-functional compound according to any one of claims 1 to 4, wherein R ¹ And R is ² Each is H.

6. The amine-functional compound according to any one of claims 1 to 5, wherein R ³ And R is ⁴ One of them is H.

7. The amine-functional compound according to any one of claims 1 to 6, wherein, when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms.

8. The polymer of any one of claims 1 to 7, wherein when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms.

9. The amine-functional compound of any one of claims 1 to 8, wherein the polymer has cohesiveness.

10. A polymer comprising monomer units of formula 3:

wherein the method comprises the steps ofIs a single bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently H or CH ₃ ；

wherein r=0 or 1 and q=0 or 1 in each monomer unit, wherein r+q=0, 1 or 2 in each monomer unit;

wherein n and m are natural numbers;

wherein n is greater than 2; and is also provided with

Wherein the repeat units in brackets are joined in a head-to-head fashion, a head-to-tail fashion, or any combination thereof.

11. A polymer comprising monomer units of formula XI:

wherein the method comprises the steps ofIs a single bond;

wherein each X ¹ 、X ² 、X ³ And X ⁴ Independently and separatelyIs H or CH ₃ ；

Wherein Y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Y ¹¹ 、Y ¹² 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is CR ¹ R ² -NR ³ R ⁴ And the rest of Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Y ¹¹ 、Y ¹² 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl or a substituted or unsubstituted heterocycle;

wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2;

wherein n and m are natural numbers;

wherein n is greater than 2;

wherein m is greater than 1; and

wherein the repeat units in brackets are joined in a head-to-head fashion, a head-to-tail fashion, a tail-to-tail fashion, or any combination thereof.

12. A polymer according to claim 10 or 11, wherein the monomer units are connected in a head-to-head manner.

13. The polymer of any one of claims 10 to 12, wherein X ¹ 、X ² 、X ³ And X ⁴ Each is H.

14. The polymer of any one of claims 10 to 12, wherein X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ 。

15. The polymer of any one of claims 10 to 12, wherein X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ 。

16. The polymer of any one of claims 10 to 15, wherein R ¹ And R is ² Each is H.

17. The polymer of any one of claims 10 to 16, wherein R ³ And R is ⁴ One of them is H.

18. The polymer of any one of claims 10 to 17, wherein when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms.

19. The polymer of any one of claims 10 to 18, wherein when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ Is a ring of (2)The carbon atoms are also substituted with hydrogen atoms.

20. The polymer of any one of claims 10 to 19, wherein the polymer has adhesive properties.

21. The polymer of claim 10, which is an amine-functionalized polyalkyl, wherein the polyalkyl comprises:

where n is a natural number greater than 2.

22. The polymer of claim 21, wherein the amine-functionalized polyalkyleneoxide has adhesion.

23. The amine-functional compound of claim 1, wherein the compound is a polyalkylene of formula 5:

wherein X is ¹ 、X ² 、X ³ And X ⁴ Each independently is H or CH ₃ ；

Wherein Y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Z ¹ And Z ² Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl or a substituted or unsubstituted heterocycle;

Wherein R is ^a 、R ^b 、R ^c And R is ^d Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group, provided that R ^a And R is ^b At least one of which is not H; or wherein R is ^b And R is ^a To form a ring portion, or wherein R ^a And R is ^b One of which is with R ^c And R is ^d To form a ring portion;

wherein n is a natural number greater than 2; and is also provided with

24. The amine-functional compound of claim 23, wherein X ¹ 、X ² 、X ³ And X ⁴ Each is H.

25. The amine-functional compound of claim 23, wherein X ¹ 、X ² 、X ³ And X ⁴ Only one of them is CH ₃ 。

26. The amine-functional compound of claim 23, wherein X ¹ And X ³ Each is H, X ² And X ⁴ Each is CH ₃ 。

27. The amine-functional compound of any one of claims 23 to 26Wherein R is ^c And R is ^d Each is H.

28. The amine-functional compound of any one of claims 23 to 27, wherein R ^b And R is ^a One of them is H.

29. The amine-functional compound of any one of claims 23 to 28, wherein the polymer has cohesiveness.

30. Use of a polymer as defined in claim 21 or an amine-functional compound as defined in any one of claims 23 to 29 as an adhesive.

31. Use of a polymer as defined in any one of claims 10 to 20 as an adhesive.

32. Use of an amine-functional compound as defined in any one of claims 1 to 9 as an adhesive.

33. Use according to claim 30, 31 or 32, wherein the adhesive is for adhesion to a substrate.

34. Use according to claim 33, wherein the substrate is teflon, glass or metal.

35. A substrate coated with a polymer as defined in claim 21 or an amine-functional compound as defined in any one of claims 23 to 29.

36. A substrate coated with an amine-functional compound as defined in any one of claims 1 to 9.

37. A substrate coated with a polymer as defined in any one of claims 10 to 20.

38. A polymer prepared by Ring Opening Metathesis Polymerization (ROMP) of an amine-functionalized cyclic olefin of formula 1:

wherein:

X ¹ 、X ² 、X ³ and X ⁴ Independently H or CH ₃ ；

Wherein Y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ At least one of them is-CR ¹ R ² -NR ³ R ⁴ And the rest of Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ And Z ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl or a substituted or unsubstituted heterocycle;

Wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1 or 2; and is also provided with

Wherein R is ¹ 、R ² 、R ³ And R is ⁴ Each independently is H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic or amine compatible protecting group, provided that R ³ And R is ⁴ At least one of which is not H; or wherein R is ³ And R is ⁴ To form a ring portion, or wherein R ³ And R is ⁴ One of which is with R ¹ And R is ² Is connected to form a ring portion, and

wherein the polymer is hydrogenated to remove double bonds in the polymer.

39. The polymer of claim 38, wherein X ¹ 、X ² 、X ³ And X ⁴ Each is H.

40. The polymer of claim 38, wherein X ¹ 、X ² 、X ³ And X ⁴ Of which only one is CH ₃ 。

41. The polymer of claim 38, wherein X ¹ And X ³ Each is H, and X ² And X ⁴ Each is CH ₃ 。

42. The polymer of any one of claims 38 to 41, wherein R ¹ And R is ² Each is H.

43. The polymer of any one of claims 38 to 42, wherein R ³ And R is ⁴ One of them is H.

44. The polymer of any one of claims 38 to 43, wherein when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When and replace with-CR ¹ R ² -NR ³ R ⁴ At least one ring carbon atom adjacent to the ring carbon atom of (c) is substituted with two H atoms.

45. The polymer of any one of claims 38 to 44, wherein when Y ³ is-CR ¹ R ² -NR ³ R ⁴ When Y is ¹ And Y ² Each is H; and Y is ⁵ And Y ⁶ Each is H.

46. The polymer of any one of claims 38 to 45, wherein when Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Z ¹ 、Z ² 、Z ³ Or Z is ⁴ is-CR ¹ R ² -NR ³ R ⁴ When substituted with-CR ¹ R ² -NR ³ R ⁴ The ring carbon atoms of (2) are also substituted with hydrogen atoms.

47. The polymer of any one of claims 38 to 46, wherein Y ³ is-CR ¹ R ² -NR ³ R ⁴ And Y is ⁴ Is H.

48. The polymer of any of claims 38 to 47, wherein the polymer is prepared by ROMP of a mixture of different amine-functionalized cyclic olefins of formula 1.

49. The polymer of any one of claims 38 to 48, wherein the monomer units polymerize head-to-head, head-to-tail, tail-to-tail, or any combination thereof.

50. The polymer of any one of claims 38 to 49, wherein the amine-functionalized cyclic olefin of formula 1 is prepared by: the method comprises contacting a cyclic olefin with a moiety comprising a secondary amine in the presence of a catalytic complex based on a group 5 metal to obtain an amine-functionalized cyclic olefin of formula 1.

51. The polymer of claim 50, wherein the cyclic olefin is cyclooctadiene.

52. The polymer of claim 50 or 51, wherein the group 5 metal-based catalytic complex has the structure of formula I:

wherein:

R ⁵ and R is ⁶ ：

Each independently is: h is formed; with substituents or no substituentsC having substituents ₁ -C ₄₀ Linear, branched or cyclic alkyl or alkenyl or alkynyl; aryl groups with or without substituents; or a heterocyclic group having a substituent or not; or alternatively

R ⁷ is H; c with or without substituents ₁ -C ₄₀ Linear, branched or cyclic alkyl or alkenyl or alkynyl; or aryl with or without substituents; or a heterocyclic group having a substituent or not; or R is ⁷ And R is R ⁵ And/or R ⁶ Bonding to form a heterocycle;

m is a group 5 metal;

a=0 to 4 and b=0 to 4, wherein the sum of a and b is 4;

each X is a halogen substituent;

each R ⁸ Independently is: h is formed; or C with or without substituents ₁ -C ₂₀ A linear, branched or cyclic alkyl group optionally containing heteroatoms.

53. The polymer of claim 52, wherein each X is independently Cl or Br.

54. The polymer of claim 52 or 53, wherein a=1 or a=2.

55. The polymer of claim 50 or 51, wherein the group 5 metal-based catalytic complex has the structure of formula II:

wherein:

R ⁵ and R is ⁶ Each independently is: methyl, ethyl, isopropyl, cyclohexyl, phenyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 4-methylphenyl, cocoaPiperidine optionally having a substituent, pyrrolidine optionally having a substituent, or morpholine optionally having a substituent; or R is ⁵ And R is ⁶ Are bonded to each other so as to form, together with the nitrogen atom to which they are bonded, a 6-membered ring optionally having a substituent;

R ⁷ is phenyl, 2, 6-dimethylphenyl or 2, 6-di (isopropyl) phenyl; or R is ⁷ And R is R ⁵ And/or R ⁶ Are bonded to each other so as to form, together with the nitrogen atom to which they are bonded, a 5-membered ring optionally having a substituent;

each X is independently Cl or Br;

a=1 or 2 and b= (4-a); and is also provided with

56. The polymer of claim 50 or 51, wherein the group 5 metal-based catalytic complex is:

or chlorotris (dimethylamido) (kappa) ² -N, O-3-methyl-2-pyridine) tantalum (V).

57. A polymer as in claim 56 wherein the group 5 metal-based catalytic complex is chlorotris (dimethylamido) (kappa) ² -N, O-3-methyl-2-pyridine) tantalum (V).

58. The polymer of any one of claims 38 to 57, wherein the polymer has adhesive properties.

59. Use of a polymer according to any one of claims 38 to 58 as an adhesive.

60. The use of claim 59, wherein the adhesive is for adhering to a substrate.

61. The use of claim 60, wherein the substrate is Teflon, glass or metal.